1. Field of the Invention
The present invention relates to a catalyst and to a process for preparing color-reduced polyisocyanates containing isocyanurate groups.
2. Discussion of the Background
For high-quality one- and two-component polyurethane coating materials possessing good light and weathering stability, polyisocyanate mixtures containing isocyanurate groups and uretdione groups are typically used as the isocyanate component.
For the preparation of polyisocyanates containing isocyanurate groups and uretdione groups, which are suitable as raw materials or polyurethane coating formulations, a variety of processes are known. These processes typically differ in the selection of the trimerization catalysts or in the selection of the organic isocyanates to be used in the oligomerization reaction (cf., e.g., GB 1 391 066, EP-A-0 082 987, DE-A 39 02 078, EP-A-0 339 396, EP-A-0 224 165).
Suitable isocyanates used for trimerization, examples of which include aromatic, cycloaliphatic and aliphatic polyisocyanates having a functionality of two or more, can be prepared by various kinds of processes (Annalen der Chemie 562 (1949) pages 75 ff.). Those which have proven particularly suitable in industry include preparation by phosgenation of organic polyamines to the corresponding polycarbamoyl chlorides and the thermal cleavage of the chlorides into organic polyisocyanates and hydrogen chloride. Alternatively, organic polyisocyanates can be prepared without the use of phosgene, i.e., by phosgene-free processes. According to EP-A-0 126 299 (U.S. Pat. No. 4,596,678), EP-A-126 300 (U.S. Pat. No. 4,596,679) and EP-A-355 443 (U.S. Pat. No. 5,087,739), for example, (cyclo)aliphatic diisocyanatesxe2x80x94such as 1,6-hexa-methylenediisocyanate (HDI) and/or isomeric aliphatic diisocyanates having 6 carbon atoms in the alkylene radical, and 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane (isophorone diisocyanate or IPDI)xe2x80x94can be prepared by reacting (cyclo)aliphatic diamines with urea and alcohols to give (cyclo)aliphatic biscarbamic esters and thermally cleaving these esters into the corresponding diisocyanates and alcohols. The synthesis takes place continuously in a circulation process and in the presence, if desired, of N-unsubstituted carbamic esters, dialkyl carbonates, and other byproducts returned from the reaction process.
Examples of catalysts which can be used for the trimerization of isocyanates to give the desired polyisocyanates containing isocyanurate groups and uretdione groups include tertiary amines, phosphines, alkali metal phenoxides, aminosilanes, quaternary ammonium hydroxides, and quaternary ammonium carbonates. Highly suitable oligomerization catalysts are hydroxides, halides or carboxylates of hydroxyalkylammonium ions (cf., e.g. EP-A-0 351 873, U.S. Pat. No. 5,290,902), alkali metal salts, and tin salts, zinc salts and lead salts of alkylcarboxylic acids. Depending on the catalyst, it is also possible to use various cocatalysts such as, for example, OH-functionalized compounds or Mannich bases comprising secondary amines and aldehydes and/or ketones.
For the oligomerization, the (cyclo)aliphatic diisocyanates are reacted in the presence of the catalyst, with or without the use as solvents and/or auxiliaries, until the desired conversion is attained. Partial trimerization is one of the terms used in this context, since the target conversion is generally well below 100%. Subsequently, the reaction is terminated by deactivating the catalyst and the excess monomeric diisocyanate is usually separated off, generally by flash distillation or thin-film distillation. Deactivation is carried out thermally or by adding a catalyst inhibitor such as, for example, p-toluenesulfonic acid or bis(2-ethylhexyl) phosphate. Particularly advantageous in the context of the trimerization of isocycanates on the industrial scale is the use of quaternary hydroxyalkylammonium carboxylates as oligomerization catalysts. These catalysts of the choline type are thermally unstable. It is unnecessary to terminate the trimerization on reaching the desired conversion by adding catalyst inhibitors which have the potential to reduce the quality. Instead, the controlled thermal deactivation permits optimum process control. The thermal instability is also advantageous from the standpoint of process safety. Uncontrolled xe2x80x9crunawayxe2x80x9d of the reaction is impossible, provided the amount of catalyst metered in remains below a multiple of the usual amount.
Depending on the type of catalyst used and the reaction temperature, the resulting polyisocyanates have different proportions of isocyanurate groups and/or uretdione groups. The products are usually clear, although products with a more or less strong yellow coloration may also be obtained depending on the type of catalyst, quality of disocyanate, temperature of reaction and reaction regime. For the preparation of high-quality polyurethane coating materials, however, products having a very low color number are desired.
The unwanted yellow also occurs when the otherwise highly advantageous quaternary hydroxyalkylammonium carboxylates are used (vide supra), so that there is a specific requirement for improvement in this context. Surprisingly, it has now been found that, in comparison to other catalysts of this type, specific quaternary hydroxyalkylammonium carboxylates provide polyisocyanates, which contain isocyanurate groups, having-markedly improved color quality.
It is an object of the present invention to provide a process for preparing polyisocyates that avoids the problems described above.
This and other objects of the invention have been achieved by the present invention, the first embodiment of which provides a process for preparing color-reduced polyisocyanates containing isocyanurate groups, which process includes:
trimerizing at least one diisocyanate in the presence of 0.04-2% by weight, based on the weight of the diisocyanate, at least one trimerization catalyst of the formula (I): 
and wherein:
A, B, C, D and E independently of one another or simultaneously are hydrogen, chloro, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkoxycarbonyl, hydroxyl, (R5)3SiOxe2x80x94, (R5)2Nxe2x80x94, COOH, (R5)2Nxe2x80x94CH2xe2x80x94 or phenyl, it being possible for any two adjacent A, B, C, D and E radicals to form a conjoint 5- or 6-membered saturated or unsaturated ring which may optionally and additionally include N, S or O as heteroatom;
F is hydrogen or methyl;
R2 and R3 independently of one another or simultaneously are C1-C4 alkyl, C2-C6 hydroxyalkyl with the hydroxyl group in position 2 relative to the quaternary nitrogen or R1;
R4 is hydrogen, methyl, C2-C10 alkyl, C3-C8 cycloalkyl or C2-C12 alkoxy;
R5 is C1-C4 alkyl;
Yxe2x88x92 is R6COOxe2x88x92 or OHxe2x88x92; and
R6 is hydrogen or a branched or unbranched, aliphatic or araliphatic, C1-C10 alkyl radical.
Another embodiment of the invention provides a trimerization catalyst of the formula (I): 
and where the variables are defined as follows:
A, B, C, D and E independently of one another or simultaneously are hydrogen, chloro, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkoxycarbonyl, hydroxyl, (R5)3SiOxe2x80x94, (R5)2Nxe2x80x94, xe2x80x94COOH, (R5)2Nxe2x80x94CH2xe2x80x94 or phenyl, it being possible for any two adjacent A, B, C, D and E radicals to form a conjoint 5- or 6-membered saturated or unsaturated ring which may optionally and additionally include N, S or O as heteroatom;
F is hydrogen or methyl;
R2 and R3 independently of one another or simultaneously are C1-C4 alkyl, C2-C6 hydroxyalkyl with a hydroxyl group in position 2 relative to the quaternary nitrogen in formula (I), or R1;
R4 is hydrogen, methyl, C2-C10 alkyl, C3-C8 cycloalkyl or C2-C12 alkoxy;
R5 is C1-C4 alkyl;
Yxe2x88x92 is R6COOxe2x88x92 or OHxe2x88x92; and
R6 is hydrogen or a branched or unbranched, aliphatic or araliphatic, C1-C10 alkyl radical.
Various other objects, features and attendant advantages of the present invention will be more fully appreciated as the same becomes better understood from the following detailed description of the preferred embodiments of the invention.
Preferably, the invention provides a process for preparing color-reduced polyisocyanates containing isocyanurate groups by partially trimerizing aliphatic, cycloaliphatic and/or (cyclo)aliphatic diisocyanates and subsequently separating off excess diisocyanate, which includes performing the trimerization in the presence of 0.04-2% by weight, based on the weight of the diisocyanate used, of at least one trimerization catalyst of the general formula (I) 
and where the variables are defined as follows:
A, B, C, D and E independently of one another or simultaneously are hydrogen, chloro, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkoxycarbonyl, hydroxyl, (R5)3SiOxe2x80x94, (R5)2Nxe2x80x94, xe2x80x94COOH, (R5)2Nxe2x80x94CH2xe2x80x94 or phenyl, it being possible for any two adjacent radicals from the group A, B, C, D and E to form a conjoint 5- or 6-membered saturated or unsaturated ring which may also include N, S or O as heteroatom;
F is hydrogen or methyl;
R2 and R3 independently of one another or simultaneously are C1-C4 alkyl, C2-C6 hydroxyalkyl (with the hydroxyl group in position 2 relative to the quaternary nitrogen) or R1;
R4 is hydrogen, methyl, C2-C10 alkyl, C3-C8 cycloalkyl or C2-C12 alkoxy;
R5 is C1-C4 alkyl;
Yxe2x88x92 is R6COOxe2x88x92 or OHxe2x88x92; and
R6 is hydrogen or a branched or unbranched aliphatic or araliphatic C1-C10 alkyl radical.
The invention further preferably provides a trimerization catalyst for preparing color-reduced polyisocyanates containing isocyanurate groups, of the general formula (I) 
and where the variables are defined as follows:
A, B, C, D and E independently of one another or simultaneously are hydrogen, chloro, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkoxycarbonyl, hydroxyl, (R5)3SiOxe2x80x94, (R5)2Nxe2x80x94, xe2x80x94COOH, (R5)2Nxe2x80x94CH2xe2x80x94 or phenyl, it being possible for any two adjacent radicals from the group A, B, C, D and E to form a conjoint 5- or 6-membered saturated or unsaturated ring which may also include N, S or O as heteroatom;
F is hydrogen or methyl;
R2 and R3 independently of one another or simultaneously are C1-C4 alkyl, C2-C6 hydroxyalkyl (with the hydroxyl group in position 2 relative to the quaternary nitrogen) or R1;
R4 is hydrogen, methyl, C2-C10 alkyl, C3-C8 cycloalkyl or C2-C12 alkoxy;
R5 is C1-C4 alkyl;
Yxe2x88x92 is R6COO or OHxe2x88x92; and
R6 is hydrogen or a branched or unbranched aliphatic or araliphatic C1-C10 alkyl radical.
The trimerization catalysts of the invention can be used to react diisocyanates prepared by the phosgene process or by a phosgene-free process: for example, by thermal cleavage of (cyclo)aliphatic biscarbamic esters (cf., e.g., EP-A-0 126 299 (U.S. Pat. No. 4,596,678)). Preferable suitable starting diisocyanates for the process of the invention include aliphatic, cycloaliphatic and/or (cyclo)aliphatic diisocyanates, more preferable examples being 1,4-diisocyanato-cyclohexane, 1,6-diisocyanatohexane (HDI), 1,12-diisocyanatododecane, 1-isocyanato-3,3,5-trimethylcyclo-hexane (IPDI), 4,4xe2x80x2-diisocyanatodicyclohexylmethane, 1,5-diisocyanato-2,2-dimethylpentane, 1,5-diisocyanato-2-ethyl-2-propylpentane, 1,5-diisocyanato-2-butyl-2-ethylpentane, 1,6-diisocyanato-2,4,4-trimethylhexane and 1,6-diisocyanato-2,4,4-trimethylhexane (TMDI), 1,5-diisocyanato-2-methylpentane (MPDI), and 2,5(2,6)-bis(isocyanatomethyl)bicyclo{2.2.1}heptane (NBDI). Even more preference is given to the use of HDI, IPDI, MPDI, TMDI and NBDI. Mixtures of diisocyanates are possible.
The preparation of the polyisocyanates containing isocyanurate groups by partial trimerization can take place either continuously (pipe reactor or reactor cascade) or batchwise. The catalysts of the invention are preferably used in a low concentration of between 0.04 and 2.0% by weight. The exact amount depends on the individual catalyst, on the target conversion and on the procedure, the use of stirred reactors having been found from experience to necessitate the metered addition of a larger amount of catalyst.
Under these conditions the trimerization can be carried out within 1-60 minutes. The resulting compounds have one or more isocyanurate rings. Compounds with a uretdione structure may also be found as a secondary component in small amounts. Compounds of this kind have been described in the literature.
The trimerization catalysts of the invention can be prepared by preferably reacting tertiary amines with a carboxylic acid and an oxirane. The molar ratio, with respect of the functionalities of the reactants, should be approximately 1:1:1; an excess of 20 mol % being with no significantly deleterious effect on catalyst performance, irrespective of the choice of the excess components. The reaction temperature is preferably between 10xc2x0 C. and 80xc2x0 C., more preferably between 20xc2x0 C. and 50xc2x0 C. The reaction can be conducted in the presence or absence of solvents. Examples of preferred solvents are ethylene glycol, tetrahydrofuran, 1-butanol, methanol, and benzyl alcohol.
Preferable examples of tertiary amines suitable in principle are N,N-dimethyl-2-methoxybenzylamine, N,N-dimethyl-3-methoxybenzylamine, N,N-dimethyl-4-methoxy-benzylamine, N,N-dimethyl-2,3-dimethoxybenzylaniine, N,N-dimethyl-3-4-dimetboxybenzylaxnine, N,N-dimethyl-3,5-dimethoxybenzylamine, N,N-dimethylbenzylamine, N,N-di-ethylbenzylaniine-4-carboxylic acid, 4-rnethoxycarbonyl-N,N-dimethylbenzylamine, 4-ethoxycarbonyl-N,N-diinethylbenzylamine, 3-(N,N-di-ethylaminomethyl)-N,N dimzthylcnzylamine dimethylbenzylaxnine, 2-phenylethyldimethylamine, 1-phenylethyldiethylamine, 4-hydroxy-N,N-dimethylbenzylamine, 4-trimethylsiloxy-N,N-dimetbylbenzylaniine and N,N-dimethylnaphthvlamine.
Preferable examples of suitable carboxylic acids are pivalic acid, hexanoic acid, acetic acid, 2-ethylhexanoic acid, propanoic acid, adipic acid, succinic acid and oleic acid.
Preferable oxiranes are aliphatic or araliphatic compounds having 1,2-epoxide groups; that is, for example, ethylene oxide, propylene oxide, 1,2-butylene oxide, 1,2-dodecene oxide, and 2,2-dimethyloxirane. The oxiranes can also be functionalized epoxy compounds such as, for example, 2,3-epoxypropyl isopropyl ether.
In order to prepare polyisocyanates containing isocyanurate groups, the catalysts of the invention are used preferably in small amounts. The exact amount can readily be determined by experiment and depends on the catalytic activity of the individual catalyst, on the target conversion and on the procedure.
In accordance with the invention, the hydroxyalkylammonium carboxylates of the formula I are preferably used in an amount of 0.04-2% by weight, more preferably 0.06-1.5% by weight, and even more preferably between 0.08 and 1.4% by weight based on the weight of the (cyclo)aliphatic diisocyanate used.
The process of the invention is preferably conducted at temperatures of between 35xc2x0 C. and 185xc2x0 C. Below 35xc2x0 C., the amount of catalyst required for the trimerization has been found from experience to be so great that color problems may result. At temperatures above 185xc2x0 C., there may likewise be unwanted discoloration of the polyisocyanates containing isocyanurate groups. Trimerization preferably takes place in the presence of the catalysts of the invention at temperatures between 50xc2x0 C. and 175xc2x0 C.
In accordance with the invention, the trimerization of the diisocyanates is carried out either batchwise or continuously.
In the case of the batch process, a stirred reactor is preferably used. In this case, the mixture of diisocyanate and catalyst are charged to the reactor usually at room temperature. Subsequently, the temperature of the reaction mixture is raised to 35-140xc2x0 C., and preferably to 50-110xc2x0 C., in order to initiate the trimerization. Alternatively, the catalyst can be metered in after the diisocyanate has reached the necessary temperature for the reaction. The trimerization is exothermic, and the catalyst is destroyed in the course of the reaction.
Continuous trimerization is preferably conducted in a reaction coil with continuous, simultaneous metered addition of the diisocyanate and of the trimerization catalyst at from 40 to 120xc2x0 C. over a period of from 1 to 7 minutes. In a reaction pipe with a small diameter, high flow rates are achieved. Furthermore, it is very advantageous to heat the diusocyanate/catalyst mixture to about 50 to 60xc2x0 C. before entry into the reaction pipe. An especially important factor is the metered addition of the catalyst. It is particularly preferable to mix the starting materials thoroughly prior to entry into the reaction coil. For more precise metering with small amounts of catalyst, and in order to generate a better quality of thorough mixing, it can be advantageous to dissolve the catalyst in an appropriate organic solvent. Appropriate solvents are in principle those in which the catalyst is readily soluble. Preferably, however, the use of solvents is very largely dispensed with.
The temperature of the sections of the reaction coil is judiciously chosen such that the preheat zone is at about 40 to 60xc2x0 C., the reaction zone at from 70 to 120xc2x0 C., preferably from 70 to 100xc2x0 C., and the cooling zone at from 20 to 40xc2x0 C. The optimum temperature conditions must in each case be adapted to the required conditions for the diisocyanate to be trimerized.
In order to remove unreacted diisocyanate, the reaction mixture is subjected to flash evaporation or short path distillation.
Preferable starting compounds appropriate for the trimerization are diisocyanates having aliphatic, cycloaliphatic or aliphatic and cycloaliphatic isocyanate groups which have been prepared by the phosgene process or by a phosgene-free process, or else mixtures of such diisocyanates. Suitable aliphatic diisocyanates have preferably 3 to 16, with particular preference 4 to 12, carbon atoms in their linear or branched alkylene substructure. Suitable low-chlorine cycloaliphatic diisocyanates have preferably 4 to 18, with particular preference 6 to 15, carbon atoms in their cycloalkylene substructure. Specific examples that may be mentioned include 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), 1,6-hexamethylene diisocyanate (HDI), 2-methyl-1,5-pentamethylene diisocyanate (MPDI), 2,5(2,6)-bis(isocyanatomethyl)bicyclo{2.2.1}heptane (NBDI), and 2,2,4- or 2,4,4-trimethyl-1,6-hexamethylene diisocyanate (TMDI).
The monomer-freed isocyanurates containing isocyanurate groups and prepared in accordance with the invention represent useful intermediates for polyurethane coatings, such as leather coatings and textile coatings, and for polyurethane dispersions and adhesives, and are particularly valuable as polyisocyanate components in 1- and 2-component polyurethane systems for weather- and light-stable polyurethane coating materials. In these applications, the process products of the invention can be used either as such or else in a form in which they are blocked with blocking agents. Examples of suitable blocking agents in that case are lactams such as xcex5-caprolactam, oximes such as methyl ethyl ketoxime or butanone oxime, triazoles such as 1H-1,2,4-triazole, readily enolizable compounds such as acetoacetic esters or acetylacetone, or else malonic acid derivatives such as malonic diesters having 1-10 carbon atoms in the alcohol residues.